JP2012166154A - Dispersant for carbon material, carbon material dispersion, and carbon material composition - Google Patents
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本発明は、有機溶媒中に炭素材料を分散させるための分散剤、この分散剤を含む有機溶媒中に炭素材料を分散させた炭素材料分散液、およびこの分散液から有機溶媒を除去した炭素材料組成物に関する。 The present invention relates to a dispersant for dispersing a carbon material in an organic solvent, a carbon material dispersion in which the carbon material is dispersed in an organic solvent containing the dispersant, and a carbon material from which the organic solvent has been removed from the dispersion. Relates to the composition.
カーボンブラック（以下、ＣＢと表記する。）、カーボンナノファイバー（以下、ＣＮＦと表記する。）、カーボンナノチューブ（以下、ＣＮＴと表記する。）といった炭素材料は、強度が高く、導電性に優れているため、その特性を活かして多くの用途開発が進められている。炭素材料のうちＣＢは、インキ、塗料、樹脂等の着色剤や導電性フィラーとして、ディスプレイ部材や磁気記録部材等の電子部品に、古くから使用されている。ＣＢを利用するにあたっては、溶媒に分散させる製造工程を経て用いられることがあり、様々な分散方法が検討されてきた。この方法の一つに、共重合体を分散剤として使用している事例が挙げられる。 Carbon materials such as carbon black (hereinafter referred to as CB), carbon nanofiber (hereinafter referred to as CNF), and carbon nanotube (hereinafter referred to as CNT) have high strength and excellent electrical conductivity. Therefore, many applications are being developed taking advantage of these characteristics. Among carbon materials, CB has long been used in electronic parts such as display members and magnetic recording members as colorants such as inks, paints, and resins, and conductive fillers. In utilizing CB, it may be used through the manufacturing process to disperse in a solvent, and various dispersion methods have been studied. One example of this method is a case where a copolymer is used as a dispersant.
特許文献１には、酸性基を有する単量体とポリオキシエチレン（メタ）アクリレート構造を有する単量体からなる共重合体を分散剤として用い、ＣＢを水に分散させた顔料分散体濃厚液が開示されている（実施例１０を参照）。しかし、分散媒は水に限定されており、有機溶剤では使用することができないので、炭素材料用分散液をポリマーに混練した場合に、ポリマー物性に悪影響を与えるおそれがあり、さらに、分散媒の除去工程が煩雑になるなどの不利な点が多い。 Patent Document 1 discloses a pigment dispersion concentrated liquid in which a copolymer composed of a monomer having an acidic group and a monomer having a polyoxyethylene (meth) acrylate structure is used as a dispersant, and CB is dispersed in water. Is disclosed (see Example 10). However, since the dispersion medium is limited to water and cannot be used with an organic solvent, there is a possibility of adversely affecting the physical properties of the polymer when the carbon material dispersion is kneaded with the polymer. There are many disadvantages such as complicated removal process.
特許文献２には、酸性基を有する単量体とアルキルエステル構造を有する単量体と、必要によりこれらと共重合可能な他の単量体（ポリオキシエチレンメタクリレート等）からなる共重合体を分散剤として用い、ＣＢ等の顔料を水溶性有機溶剤に分散させたインクジェットプリンタ用インクが開示されている。しかし、金属イオンと塩を形成し易い酸性基を有する単量体が必須であるので、電子材料等への応用は困難である。 Patent Document 2 discloses a copolymer comprising a monomer having an acidic group, a monomer having an alkyl ester structure, and, if necessary, other monomers (polyoxyethylene methacrylate, etc.) copolymerizable therewith. An ink for an ink jet printer in which a pigment such as CB is dispersed in a water-soluble organic solvent as a dispersant is disclosed. However, since a monomer having an acidic group that easily forms a salt with a metal ion is essential, application to an electronic material or the like is difficult.
特許文献３には、疎水性の単量体と親水部にカルボン酸基またはその塩を有する単量体と必要によりこれらと共重合可能な他のモノマー（ポリオキシエチレンメタクリレート等）からなる共重合体を分散剤として用い、ＣＢ等の水不溶性色材を水溶性有機溶媒に分散させたインクジェット記録用インクが開示されている。しかし、親水部にカルボン酸基またはその塩を有する単量体が必須であるので、特許文献２と同様に、電子材料等への応用は困難である。 Patent Document 3 discloses a copolymer consisting of a hydrophobic monomer, a monomer having a carboxylic acid group or a salt thereof in the hydrophilic portion, and, if necessary, other monomers (polyoxyethylene methacrylate, etc.) copolymerizable therewith. An inkjet recording ink is disclosed in which a coalescence is used as a dispersant and a water-insoluble colorant such as CB is dispersed in a water-soluble organic solvent. However, since a monomer having a carboxylic acid group or a salt thereof is essential in the hydrophilic portion, it is difficult to apply to an electronic material or the like as in Patent Document 2.
近年、ＣＮＦやＣＮＴ等の平均粒径または直径が比較的小さい炭素材料が新たに注目を集めており、これらの炭素材料はＣＢよりも比重が低く、強度が高く、導電性に優れているため、多くの用途開発が期待されている。しかし、これらの炭素材料は他の炭素材料と異なり、グラフェン構造以外の構造、例えばカルボン酸やアルデヒドなどが分子内に極端に少ない。そのため、他の分子との親和性が悪く、水や有機溶媒、高分子材料に特に分散しにくいことから、平均粒径または直径が比較的小さい炭素材料を分散する技術が求められている。 In recent years, carbon materials having a relatively small average particle diameter or diameter, such as CNF and CNT, have attracted a lot of attention. These carbon materials have lower specific gravity, higher strength, and excellent electrical conductivity than CB. Many applications are expected to be developed. However, unlike other carbon materials, these carbon materials have extremely few structures other than the graphene structure, such as carboxylic acid and aldehyde, in the molecule. Therefore, since it has poor affinity with other molecules and is particularly difficult to disperse in water, an organic solvent, or a polymer material, a technique for dispersing a carbon material having a relatively small average particle diameter or diameter is required.
特許文献４には、メチルメタクリレートなどの短鎖アルキルメタクリレートを含むメタクリル樹脂にＣＢやＣＮＴを分散させたバインダー樹脂に対して、グリセリンといった水酸基を３個以上有するポリオールを分散剤として用いたペースト組成物が開示されている。しかし、有機溶媒中で分散液とした場合には、均一で安定な分散液を得ることはできなかった。 Patent Document 4 discloses a paste composition in which a polyol having three or more hydroxyl groups such as glycerin is used as a dispersant for a binder resin in which CB and CNT are dispersed in a methacrylic resin containing a short-chain alkyl methacrylate such as methyl methacrylate. Is disclosed. However, when the dispersion is used in an organic solvent, a uniform and stable dispersion cannot be obtained.
本発明は、炭素材料を有機溶媒中で均一かつ安定に分散することができる炭素材料用分散剤、有機溶媒中で炭素材料が均一に分散した炭素材料分散液、ならびに有機溶媒中で分散性に優れた炭素材料組成物を提供することを目的とする。 The present invention relates to a dispersant for a carbon material that can uniformly and stably disperse a carbon material in an organic solvent, a carbon material dispersion in which the carbon material is uniformly dispersed in the organic solvent, and a dispersibility in the organic solvent. An object is to provide an excellent carbon material composition.
上記課題を解決するために鋭意検討した結果、本発明者らは、特定のアルキル基とオキシアルキレン基を側鎖に有する（メタ）アクリル共重合体を炭素材料用分散剤として用いることによって、有機溶媒中で均一かつ安定に炭素材料を分散できることを見出し、本発明を完成した。 As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that by using a (meth) acrylic copolymer having a specific alkyl group and an oxyalkylene group in the side chain as a dispersant for a carbon material, The present inventors have found that a carbon material can be dispersed uniformly and stably in a solvent.
すなわち、本発明の炭素材料用分散剤は、式１で表される構成単位（ａ１）と式２で表される構成単位（ａ２）からなり、（ａ１）と（ａ２）の質量比（ａ１）／（ａ２）が９０／１０〜１０／９０であり、重量平均分子量が3,000 〜500,000 である共重合体（Ａ）からなる。 That is, the dispersant for carbon material of the present invention is composed of the structural unit (a1) represented by Formula 1 and the structural unit (a2) represented by Formula 2, and the mass ratio (a1) between (a1) and (a2) ) / (A2) is 90/10 to 10/90, and the copolymer (A) has a weight average molecular weight of 3,000 to 500,000.
〔式（１）中、Ｒ1は水素原子またはメチル基を、Ｒ2は炭素数１６〜２２のアルキル基を示す。〕 Wherein (1), R 1 represents a hydrogen atom or a methyl group, R 2 represents an alkyl group having 16 to 22 carbon atoms. ]
〔式（２）中、Ｒ3は水素原子またはメチル基を、Ｒ4は水素原子または炭素数１〜２２のアルキル基を表す。また、ＡＯは炭素数２〜４のオキシアルキレン基を、ｎはオキシアルキレン基の付加モル数を示し、１〜１００の整数である。〕 Wherein (2), the R 3 is a hydrogen atom or a methyl group, R 4 represents a hydrogen atom or an alkyl group having 1 to 22 carbon atoms. AO represents an oxyalkylene group having 2 to 4 carbon atoms, n represents an added mole number of the oxyalkylene group, and is an integer of 1 to 100. ]
また、本発明の炭素材料分散液は、本発明の炭素材料用分散剤である共重合体（Ａ）、炭素材料（Ｂ）および有機溶媒（Ｃ）を含有する。 Moreover, the carbon material dispersion liquid of this invention contains the copolymer (A) which is a dispersing agent for carbon materials of this invention, a carbon material (B), and an organic solvent (C).
炭素材料分散液のある実施形態において、炭素材料（Ｂ）が、カーボンブラック、カーボンナノチューブ、カーボンナノファイバー、カーボンナノコイル、フラーレン、炭素繊維、グラファイトからなる群から選ばれる少なくとも一つである。 In an embodiment of the carbon material dispersion, the carbon material (B) is at least one selected from the group consisting of carbon black, carbon nanotube, carbon nanofiber, carbon nanocoil, fullerene, carbon fiber, and graphite.
さらに、本発明の炭素材料組成物は、本発明の炭素材料分散液から有機溶媒（Ｃ）を除去することにより得られる炭素材料組成物である。 Furthermore, the carbon material composition of the present invention is a carbon material composition obtained by removing the organic solvent (C) from the carbon material dispersion of the present invention.
本発明の炭素材料用分散剤は、炭素材料を凝集させ難く、均一かつ安定に有機溶媒中に分散させることができる。また、本発明の炭素材料分散液は、炭素材料の分散安定性に優れる。さらに、本発明の炭素材料組成物は、有機溶媒中に容易に分散することができるため有用である。 The dispersant for carbon material of the present invention hardly aggregates the carbon material and can be uniformly and stably dispersed in the organic solvent. Moreover, the carbon material dispersion of the present invention is excellent in the dispersion stability of the carbon material. Furthermore, the carbon material composition of the present invention is useful because it can be easily dispersed in an organic solvent.
以下、本発明の実施の形態について詳細に説明する。
本発明の炭素材料用分散剤は、式１で表される構成単位（ａ１）と式２で表される構成単位（ａ２）からなり、（ａ１）と（ａ２）の質量比（ａ１）／（ａ２）が９０／１０〜１０／９０であり、重量平均分子量が3,000 〜500,000 である共重合体（Ａ）からなる。
Hereinafter, embodiments of the present invention will be described in detail.
The dispersant for carbon material of the present invention comprises a structural unit (a1) represented by formula 1 and a structural unit (a2) represented by formula 2, and a mass ratio (a1) / (a1) / (a2) (A2) is 90 / 10-10 / 90, and consists of a copolymer (A) whose weight average molecular weight is 3,000-500,000.
〔式（１）中、Ｒ1は水素原子またはメチル基を、Ｒ2は炭素数１６〜２２のアルキル基を示す。〕 Wherein (1), R 1 represents a hydrogen atom or a methyl group, R 2 represents an alkyl group having 16 to 22 carbon atoms. ]
〔式（２）中、Ｒ3は水素原子またはメチル基を、Ｒ4は水素原子または炭素数１〜２２のアルキル基を表す。また、ＡＯは炭素数２〜４のオキシアルキレン基を、ｎはオキシアルキレン基の付加モル数を示し、１〜１００の整数である。〕 Wherein (2), the R 3 is a hydrogen atom or a methyl group, R 4 represents a hydrogen atom or an alkyl group having 1 to 22 carbon atoms. AO represents an oxyalkylene group having 2 to 4 carbon atoms, n represents an added mole number of the oxyalkylene group, and is an integer of 1 to 100. ]
式（１）中、Ｒ1は水素原子またはメチル基である。Ｒ2は炭素数１６〜２２のアルキル基、特に飽和アルキル基であり、パルミチル基、イソパルミチル基、ステアリル基、イソステアリル基、ベヘニル基、イソベヘニル基などが挙げられ、好ましくは、パルミチル基、ステアリル基、ベヘニル基である。式（１）の単量体は、例えば、アクリル酸またはメタクリル酸と、炭素数１６〜２２のアルキルアルコールとを常法にて、エステル化することにより得ることができる。 In formula (1), R 1 is a hydrogen atom or a methyl group. R 2 is an alkyl group having 16 to 22 carbon atoms, particularly a saturated alkyl group, and includes a palmityl group, an isopalmityl group, a stearyl group, an isostearyl group, a behenyl group, an isobehenyl group, and the like, preferably a palmityl group and a stearyl group. , A behenyl group. The monomer of formula (1) can be obtained, for example, by esterifying acrylic acid or methacrylic acid and an alkyl alcohol having 16 to 22 carbon atoms by a conventional method.
式（２）中、Ｒ3は水素原子またはメチル基である。Ｒ4は水素原子または炭素数１〜２２のアルキル基であり、好ましくは、水素原子、炭素数１〜１８のアルキル基、シクロアルキル基であり、メチル基、ステアリル基などが挙げられる。ＣＮＴやＣＮＦなどのほとんどがグラフェン構造である炭素材料をトルエンなどの芳香族炭化水素に分散する場合には、分散性の高さから、Ｒ4は炭素数が１〜１８のアルキル基のものが好ましく、炭素数が１８のアルキル基であるものがさらに好ましい。 In the formula (2), R 3 is a hydrogen atom or a methyl group. R 4 is a hydrogen atom or an alkyl group having 1 to 22 carbon atoms, preferably a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, or a cycloalkyl group, and examples thereof include a methyl group and a stearyl group. When carbon materials such as CNT and CNF, which are mostly graphene structures, are dispersed in aromatic hydrocarbons such as toluene, R 4 is an alkyl group having 1 to 18 carbon atoms because of its high dispersibility. Preferably, it is an alkyl group having 18 carbon atoms.
式（２）中、ＡＯは炭素数２〜４のオキシアルキレン基を示しており、例えば、オキシエチレン基、オキシプロピレン基、オキシブチレン基、オキシテトラメチレン基などが挙げられ、好ましくは、オキシエチレン基、オキシプロピレン基、オキシブチレン基である。これらのオキシアルキレン基は単独でも２種以上の混合でもよく、混合の場合、ブロック共重合でも、ランダム共重合のどちらでも構わない。オキシアルキレン基の付加モル数ｎは、１〜１００、好ましくは２〜６０、より好ましくは３〜５０の数であり、１００より大きくなると分散安定化能が低下することがある。オキシアルキレン基の平均付加モル数ｍとしては、２〜８０、好ましくは３〜５０、より好ましくは４〜３５である。 In the formula (2), AO represents an oxyalkylene group having 2 to 4 carbon atoms, and examples thereof include an oxyethylene group, an oxypropylene group, an oxybutylene group, and an oxytetramethylene group, preferably oxyethylene Group, oxypropylene group and oxybutylene group. These oxyalkylene groups may be used singly or as a mixture of two or more. In the case of mixing, either block copolymerization or random copolymerization may be used. The added mole number n of the oxyalkylene group is 1 to 100, preferably 2 to 60, more preferably 3 to 50, and if it exceeds 100, the dispersion stabilizing ability may be lowered. The average added mole number m of the oxyalkylene group is 2 to 80, preferably 3 to 50, more preferably 4 to 35.
式（２）の単量体は、例えば、アクリル酸またはメタクリル酸と、ポリオキシアルキレンモノアルキルエーテルとを常法にて、エステル化することにより得ることができる。また、アクリル酸またはメタクリル酸に、酸性触媒もしくはアルカリ性触媒を用いて、オキシアルキレンを直接付加することによっても得ることができる。 The monomer of the formula (2) can be obtained, for example, by esterifying acrylic acid or methacrylic acid and polyoxyalkylene monoalkyl ether by a conventional method. It can also be obtained by directly adding oxyalkylene to acrylic acid or methacrylic acid using an acidic catalyst or an alkaline catalyst.
本発明における式１で表される構成単位（ａ１）と式２で表される構成単位（ａ２）からなる共重合体（Ａ）は、ブロック共重合、ランダム共重合、グラフト重合など、その構成単位の配列には、特に制限はない。共重合体（Ａ）は、公知の重合方法により得ることができ、例えば、式１の単量体と式２の単量体をトルエンなどの芳香族炭化水素中、ジアシルパーオキサイド、パーオキシジカーボネート、パーオキシエステル、パーオキシケタール、ジアルキルパーオキサイド、ハイドロパーオキサイドなどの過酸化物系重合開始剤、アゾイソブチロニトリル、アゾイソバレロニトリルなどのアゾ系重合開始剤などを用いて重合して得ることができる。 The copolymer (A) composed of the structural unit (a1) represented by the formula 1 and the structural unit (a2) represented by the formula 2 in the present invention has a constitution such as block copolymerization, random copolymerization, and graft polymerization. There is no particular limitation on the arrangement of units. The copolymer (A) can be obtained by a known polymerization method. For example, a monomer of formula 1 and a monomer of formula 2 are mixed in an aromatic hydrocarbon such as toluene, diacyl peroxide, peroxydi. Polymerized using peroxide polymerization initiators such as carbonates, peroxyesters, peroxyketals, dialkyl peroxides and hydroperoxides, and azo polymerization initiators such as azoisobutyronitrile and azoisovaleronitrile. Can be obtained.
共重合体（Ａ）における構成単位（ａ１）と構成単位（ａ２）の質量比（ａ１）／（ａ２）は、９０／１０〜１０／９０であり、好ましくは４０／６０〜８０／２０である。また、共重合体（Ａ）の重量平均分子量は、3,000 〜500,000 であり、好ましくは5,000 〜100,000 、より好ましくは10,000〜50,000である。 The mass ratio (a1) / (a2) of the structural unit (a1) to the structural unit (a2) in the copolymer (A) is 90/10 to 10/90, preferably 40/60 to 80/20. is there. The weight average molecular weight of the copolymer (A) is 3,000 to 500,000, preferably 5,000 to 100,000, more preferably 10,000 to 50,000.
本発明の炭素材料分散液は、本発明の炭素材料用分散剤である共重合体（Ａ）、炭素材料（Ｂ）および有機溶媒（Ｃ）を含有する。本発明の炭素材料分散液は、例えば、共重合体（Ａ）を、有機溶媒（Ｃ）である分散媒に溶解もしくは分散させ、得られた溶液または分散液に炭素材料（Ｂ）を所定量入れた後に、撹拌などの操作を行う方法により得られる。炭素材料分散液は、炭素材料（Ｂ）の凝集がほとんど無く、均一かつ安定的に炭素材料（Ｂ）が分散している。 The carbon material dispersion of the present invention contains a copolymer (A), a carbon material (B), and an organic solvent (C) that are the dispersant for carbon materials of the present invention. In the carbon material dispersion of the present invention, for example, the copolymer (A) is dissolved or dispersed in a dispersion medium that is an organic solvent (C), and a predetermined amount of the carbon material (B) is added to the obtained solution or dispersion. After putting, it is obtained by a method of performing an operation such as stirring. The carbon material dispersion has almost no aggregation of the carbon material (B), and the carbon material (B) is uniformly and stably dispersed.
本発明で使用する炭素材料（Ｂ）としては、例えば、ＣＢ、ＣＮＦ、ＣＮＴ、カーボンナノコイル（以下、ＣＮＣと表記する。）、フラーレン、炭素繊維、グラファイトなどが挙げられる。以下に、ＣＢ、ＣＮＦ、ＣＮＴ、ＣＮＣに関して具体的に説明する。 Examples of the carbon material (B) used in the present invention include CB, CNF, CNT, carbon nanocoil (hereinafter referred to as CNC), fullerene, carbon fiber, and graphite. Hereinafter, CB, CNF, CNT, and CNC will be specifically described.
ＣＢは、黒色または帯灰黒色の炭素粉末であり、有機物を不完全燃焼または熱分解することにより得られる。本発明で使用するＣＢは、市販のファーネスブラック、チャンネルブラック、アセチレンブラック、ケッチェンブラックなどが挙げられる。また、酸化処理したカーボンブラックや、中空カーボンなども使用できるが、表面官能基の少ない中性カーボンが好ましい。ＣＢの大きさ等は、特に限定されないが、平均粒径は、好ましくは０．０１〜１μｍ、さらに好ましくは０．０１〜０．２μｍである。 CB is black or blackish black carbon powder, and is obtained by incomplete combustion or thermal decomposition of organic matter. Examples of the CB used in the present invention include commercially available furnace black, channel black, acetylene black, and ketjen black. Further, oxidized carbon black, hollow carbon, and the like can be used, but neutral carbon with few surface functional groups is preferable. The size of CB and the like are not particularly limited, but the average particle size is preferably 0.01 to 1 μm, more preferably 0.01 to 0.2 μm.
ＣＮＦは、一般的に、平均直径が８０〜数百ｎｍの繊維状物質炭素であり、炭素を原料とし、主に触媒化学気相析出法で得られる。本発明で使用するＣＮＦの大きさ等は特に限定されないが、典型的には、平均直径が８０〜数百ｎｍ、平均アスペクト比が１００〜２５０であり、好ましくは平均直径が１００〜２００ｎｍ、平均アスペクト比が５０〜１００、より好ましくは平均直径が１００〜１５０ｎｍ、平均アスペクト比が６０〜１００である。 CNF is generally a fibrous substance carbon having an average diameter of 80 to several hundred nm, and is obtained mainly by catalytic chemical vapor deposition using carbon as a raw material. The size or the like of CNF used in the present invention is not particularly limited, but typically, the average diameter is 80 to several hundred nm, the average aspect ratio is 100 to 250, and preferably the average diameter is 100 to 200 nm. The aspect ratio is 50 to 100, more preferably the average diameter is 100 to 150 nm, and the average aspect ratio is 60 to 100.
ＣＮＴは、平均直径０．５〜５０ｎｍ、長さμｍオーダーの筒状炭素であり、通常、化学気相成長法（ＣＶＤ法）、レーザー蒸発法、アーク放電法等により得られる。本発明で使用するＣＮＴは、その製造方法が限定されず、グラフェンシートが単層のものでも複数の層からなるものでも、カップ状に積み重なったものでも構わない。例として、単層カーボンナノチューブ、多層カーボンナノチューブ、カップスタック型カーボンナノチューブが挙げられる。ＣＮＴの大きさ等は、特に限定されないが、典型的には平均直径が１０〜２００ｎｍ、平均アスペクト比が５〜２５０であり、好ましくは平均直径が１０〜８０ｎｍ、平均アスペクト比が５０〜１５０、より好ましくは平均直径が１０〜５０ｎｍ、平均アスペクト比が８０〜１２０である。 CNT is cylindrical carbon having an average diameter of 0.5 to 50 nm and a length of the order of μm, and is usually obtained by a chemical vapor deposition method (CVD method), a laser evaporation method, an arc discharge method, or the like. The manufacturing method of the CNTs used in the present invention is not limited, and the graphene sheets may be a single layer, a plurality of layers, or stacked in a cup shape. Examples include single-walled carbon nanotubes, multi-walled carbon nanotubes, and cup-stacked carbon nanotubes. The size and the like of CNTs are not particularly limited, but typically the average diameter is 10 to 200 nm and the average aspect ratio is 5 to 250, preferably the average diameter is 10 to 80 nm, the average aspect ratio is 50 to 150, More preferably, the average diameter is 10 to 50 nm and the average aspect ratio is 80 to 120.
ＣＮＣは、繊維の直径が数十ｎｍ〜数百ｎｍ、コイルの径が数十ｎｍ〜数μｍの３Ｄヘリカル／らせん構造をもつ気相成長炭素繊維であり、主にアセチレンの触媒活性化熱分解法により製造される。ＣＮＣは機械的強度が高く、導電性に優れ、またコイル状であることから、バネ特性に優れているという特徴を有する。 CNC is a vapor-grown carbon fiber having a 3D helical / helical structure with a fiber diameter of several tens to several hundreds of nanometers and a coil diameter of several tens of nanometers to several μm. Manufactured by the law. CNC is characterized by high mechanical strength, excellent electrical conductivity, and a coil shape, so that it has excellent spring characteristics.
本発明で使用する有機溶媒（Ｃ）は、本発明の共重合体（Ａ）を溶解、もしくは分散するものであればよく、芳香族炭化水素、脂肪族炭化水素、脂環式炭化水素、アルコール類、カルボン酸類、エステル・ラクトン類、ケトン類、エーテル類、アミン類、アミド・ピロリドン類、ニトリル類、スルホキシド類、カーボネート類、ハロゲン化炭化水素、低分子液状モノマー類、低分子液状ポリマー類などが挙げられる。 The organic solvent (C) used in the present invention may be any one that dissolves or disperses the copolymer (A) of the present invention. Aromatic hydrocarbons, aliphatic hydrocarbons, alicyclic hydrocarbons, alcohols , Carboxylic acids, esters / lactones, ketones, ethers, amines, amides / pyrrolidones, nitriles, sulfoxides, carbonates, halogenated hydrocarbons, low molecular weight liquid monomers, low molecular weight liquid polymers, etc. Is mentioned.
芳香族炭化水素は、トルエン、キシレン、スチレンが挙げられる。脂肪族炭化水素は、ｎ−ヘキサン、ｎ−デカン、石油エーテルが挙げられる。脂環式炭化水素は、シクロヘキサン、メチルシクロヘキサンが挙げられる。アルコール類は、メタノール、イソプロパノール、シクロヘキサノール、ターピネオール、エチレングリコール、グリセリンが挙げられる。カルボン酸類は、カプリル酸、リノール酸が挙げられる。エステル・ラクトン類は、酢酸エチル、酢酸ブチル、メタクリル酸メチル、γ―ブチルラクトン、カプリロラクトン、ステアラクトンが挙げられる。ケトン類は、アセトン、メチルエチルケトン、エチルイソブチルケトンが挙げられる。エーテル類は、ジエチルエーテル、ジイソプロピルエーテル、テトラヒドロフラン、エチレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル、エチレングリコールジメチルエーテルが挙げられる。アミン類は、エチルアミン、トリエタノールアミンが挙げられる。アミド・ピロリドン類は、N,N-ジメチルホルムアミド、N,N-ジメチルアセトアミド、Ｎ−メチル−２−ピロリドンが挙げられる。ニトリル類は、アセトニトリル、プロピオニトリルが挙げられる。スルホキシド類は、N,N-ジメチルスルホキシド、テトラメチレンスルホキシドが挙げられる。カーボネート類は、炭酸ジエチル、プロピレンカーボネートが挙げられる。ハロゲン化炭化水素は、塩化メチル、クロロホルム、四塩化炭素が挙げられる。低分子液状モノマー類は、酢酸ビニルが挙げられる。低分子液状ポリマー類は、ポリエチレングリコール、ポリプロピレングリコール、ポリジメチルシロキサンが挙げられる。 Aromatic hydrocarbons include toluene, xylene, and styrene. Examples of the aliphatic hydrocarbon include n-hexane, n-decane, and petroleum ether. Examples of the alicyclic hydrocarbon include cyclohexane and methylcyclohexane. Examples of alcohols include methanol, isopropanol, cyclohexanol, terpineol, ethylene glycol, and glycerin. Examples of carboxylic acids include caprylic acid and linoleic acid. Esters and lactones include ethyl acetate, butyl acetate, methyl methacrylate, γ-butyl lactone, caprylolactone, and stealactone. Examples of ketones include acetone, methyl ethyl ketone, and ethyl isobutyl ketone. Examples of ethers include diethyl ether, diisopropyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, and ethylene glycol dimethyl ether. Examples of amines include ethylamine and triethanolamine. Examples of the amide / pyrrolidones include N, N-dimethylformamide, N, N-dimethylacetamide, and N-methyl-2-pyrrolidone. Examples of nitriles include acetonitrile and propionitrile. Examples of the sulfoxides include N, N-dimethyl sulfoxide and tetramethylene sulfoxide. Examples of carbonates include diethyl carbonate and propylene carbonate. Examples of the halogenated hydrocarbon include methyl chloride, chloroform, and carbon tetrachloride. Low molecular weight liquid monomers include vinyl acetate. Low molecular liquid polymers include polyethylene glycol, polypropylene glycol, and polydimethylsiloxane.
有機溶媒（Ｃ）は、好ましくは、芳香族炭化水素、アルコール類、ケトン類である。また、有機溶媒（Ｃ）は、単独でも２種以上混合しても使用することができる。本発明の炭素材料分散液は、必要に応じて分散媒の物性を損なわない範囲で、重合開始剤、粘度調節剤、貯蔵安定剤、湿潤剤、酸、塩基、および塩からなる群から１種以上の添加剤をさらに含むことができる。 The organic solvent (C) is preferably an aromatic hydrocarbon, an alcohol or a ketone. The organic solvent (C) can be used alone or in combination of two or more. The carbon material dispersion liquid of the present invention is one type from the group consisting of a polymerization initiator, a viscosity modifier, a storage stabilizer, a wetting agent, an acid, a base, and a salt as long as the physical properties of the dispersion medium are not impaired as required. The above additives can be further included.
本発明の炭素材料分散液を調製する方法は、特に限定されるものではないが、通常、以下の工程で行われる。まず、有機溶媒（Ｃ）１００質量部に対し、共重合体（Ａ）を０．０１〜２０質量部添加し、必要に応じて、加熱、攪拌をおこない、分散剤含有物を調製する。次に、分散剤含有物１００質量部に対し、炭素材料（Ｂ）を０．００１〜１００質量部添加する。 The method for preparing the carbon material dispersion of the present invention is not particularly limited, but is usually performed in the following steps. First, 0.01 to 20 parts by mass of the copolymer (A) is added to 100 parts by mass of the organic solvent (C), and if necessary, heating and stirring are performed to prepare a dispersant-containing material. Next, 0.001 to 100 parts by mass of the carbon material (B) is added to 100 parts by mass of the dispersant-containing material.
適した分散方法としては、炭素材料（Ｂ）の種類により異なるが、各種公知の分散技術を用いることができる。例えば、超音波照射、高圧混合、ホモジナイザー、ビーズミル、ボールミル、ロールミルなどが挙げられ、これらの分散技術を組み合わせた方法で分散をおこなっても良い。 A suitable dispersion method varies depending on the type of the carbon material (B), but various known dispersion techniques can be used. For example, ultrasonic irradiation, high-pressure mixing, a homogenizer, a bead mill, a ball mill, a roll mill, and the like can be mentioned, and dispersion may be performed by a method combining these dispersion techniques.
本発明の炭素材料分散液は、そのまま使用してもよいし、また分散液中の有機溶媒（Ｃ）を除去して、炭素材料（Ｂ）の表面に共重合体（Ａ）が付着した炭素材料組成物を調製しても良い。有機溶媒（Ｃ）が除去された炭素材料組成物とすることによって、保管や運搬が容易となり好ましい。 The carbon material dispersion liquid of the present invention may be used as it is, or carbon obtained by removing the organic solvent (C) in the dispersion liquid and attaching the copolymer (A) to the surface of the carbon material (B). A material composition may be prepared. By using a carbon material composition from which the organic solvent (C) has been removed, storage and transportation are facilitated, which is preferable.
本発明の炭素材料組成物は、本発明の炭素材料分散液から有機溶媒（Ｃ）を除去することにより、すなわち炭素材料分散液を乾燥することで得られる。乾燥方法は特に限定されるものではなく、フリーズドライ、スプレードライ、真空乾燥、エバポレーションなどが挙げられる。有機溶媒（Ｃ）を除去して得られた炭素材料組成物は、必要に応じて、再度、有機溶媒（Ｃ）中に分散させて、炭素材料（Ｂ）の再分散液にすることができる。再分散に使用する有機溶媒（Ｃ）は、通常、乾燥前の分散液中の有機溶媒（Ｃ）と同じ溶媒である。 The carbon material composition of the present invention can be obtained by removing the organic solvent (C) from the carbon material dispersion of the present invention, that is, by drying the carbon material dispersion. The drying method is not particularly limited, and examples include freeze drying, spray drying, vacuum drying, and evaporation. The carbon material composition obtained by removing the organic solvent (C) can be dispersed again in the organic solvent (C) as necessary to obtain a redispersed liquid of the carbon material (B). . The organic solvent (C) used for redispersion is usually the same solvent as the organic solvent (C) in the dispersion before drying.
以下、実施例および比較例を挙げて本発明を更に具体的に説明する。 Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples.
〔実施例１−１〕＜炭素材料用分散剤の合成＞
加熱装置、撹拌装置、窒素吹き込み管、滴下ロート、冷却管を備えた反応器に、トルエンを７００ｇ仕込み、窒素雰囲気とした後、攪拌しながら環流温度まで昇温した。昇温後、ステアリルメタクリレート４００ｇ（１．１８ｍｏｌ）、ポリオキシプロピレン（平均付加モル数１４）メタクリレート６００ｇ（０．７５ｍｏｌ）、1,1-ジ（ｔ−へキシルパーオキシ）シクロヘキサン７．９ｇ（０．０２５ｍｏｌ）をトルエン６５０ｇに溶解した溶液を反応器に２時間掛けて適下した。適下終了後、１時間環流し、1,1-ジ（ｔ−へキシルパーオキシ）シクロヘキサン０．７９ｇ（０．００２ｍｏｌ、単量体と合わせて入れた量の１／１０とする。）をトルエン５０ｇに溶解した溶液を適下ロートから、環流温度で反応器に３０分掛けて適下した。さらに、２時間環流し、次に、４０℃でエバポレーション、１０５℃で真空乾燥をおこなうことによりトルエンを除去し、本実施例に係る分散剤を得た。表１に実施例または比較例で用いる単量体と構成単位（ａ１）、（ａ２）の関係を記し、表２に分散剤（実施例の分散剤を表わす。）または比較剤（比較例の分散剤を表わす。）の重合条件と重量平均分子量を記した。
[Example 1-1] <Synthesis of dispersant for carbon material>
A reactor equipped with a heating device, a stirrer, a nitrogen blowing tube, a dropping funnel, and a cooling tube was charged with 700 g of toluene to form a nitrogen atmosphere, and then the temperature was raised to the reflux temperature while stirring. After the temperature increase, stearyl methacrylate 400 g (1.18 mol), polyoxypropylene (average addition mole number 14) methacrylate 600 g (0.75 mol), 1,1-di (t-hexylperoxy) cyclohexane 7.9 g (0 .025 mol) in 650 g of toluene was appropriately placed in the reactor over 2 hours. At the end of the reaction, reflux for 1 hour and 0.79 g of 1,1-di (t-hexylperoxy) cyclohexane (0.002 mol, 1/10 of the amount added together with the monomer). A solution dissolved in 50 g of toluene was appropriately reduced from a suitable funnel over 30 minutes at the reflux temperature in the reactor. Further, the mixture was refluxed for 2 hours, then evaporated at 40 ° C. and vacuum dried at 105 ° C. to remove toluene, thereby obtaining a dispersant according to this example. Table 1 shows the relationship between the monomers used in Examples or Comparative Examples and the structural units (a1) and (a2), and Table 2 shows dispersants (representing the dispersants of Examples) or comparative agents (Comparative Examples). The polymerization conditions and the weight average molecular weight are shown.
〔実施例１−２〜１−５、比較例１−１〜１−５〕＜分散剤および比較剤の合成＞
実施例１−１で用いた原料と条件を、表１および表２に示す原料と条件に変更し、重合開始剤の種類と量を適宜合わせた以外は、実施例１−１と同様の方法を用いて分散剤および比較剤を得た。
[Examples 1-2 to 1-5, Comparative Examples 1-1 to 1-5] <Synthesis of dispersant and comparative agent>
The same method as in Example 1-1, except that the raw materials and conditions used in Example 1-1 were changed to the raw materials and conditions shown in Tables 1 and 2 and the type and amount of the polymerization initiator were appropriately adjusted. Were used to obtain a dispersant and a comparative agent.
〔参考例１〕＜重量平均分子量の測定＞
実施例１−１〜１−５と、比較例１−１〜１−５を、ゲルパーミエイション・クロマトグラフィー法を用いて、以下の条件で、ポリスチレン換算の重量平均分子量を測定した。結果を表２に併せて記す。
[Reference Example 1] <Measurement of weight average molecular weight>
Examples 1-1 to 1-5 and Comparative Examples 1-1 to 1-5 were measured for polystyrene-reduced weight average molecular weight under the following conditions using gel permeation chromatography. The results are also shown in Table 2.
測定機器：ＨＬＣ−8220ＧＰＣ（東ソー株式会社製）、
検出器：ＲＩ−8022 Refractive Index Detector（東ソー株式会社製）、
カラム：ＫＦ−805 Ｌ（Ｓｈｏｄｅｘ社製）：１本、
カラム温度：４０℃、
溶離液：テトラヒドロフラン、
流速：１．０ｍＬ／分、
標準物質：ポリスチレン、
インジェクション量：１００μＬ
Measuring instrument: HLC-8220GPC (manufactured by Tosoh Corporation),
Detector: RI-8022 Refractive Index Detector (manufactured by Tosoh Corporation),
Column: KF-805 L (manufactured by Shodex): 1
Column temperature: 40 ° C
Eluent: tetrahydrofuran,
Flow rate: 1.0 mL / min,
Reference material: polystyrene,
Injection volume: 100 μL
〔実施例２−１〕＜ＣＢ分散液の調製＞
カーボンブラック（＃40、三菱化学（株）製、平均粒子径２４ｎｍ）５．０ｇに実施例１−１の分散剤０．２ｇを添加し、スターラーでかき混ぜながらメチルエチルケトン２２．４ｇを加え、ＣＢ分散液を調製した。表３の実施例２−１に、分散剤、分散媒および分散媒添加量を記した。
[Example 2-1] <Preparation of CB dispersion>
0.2 g of the dispersant of Example 1-1 was added to 5.0 g of carbon black (# 40, manufactured by Mitsubishi Chemical Corporation, average particle size: 24 nm), and 22.4 g of methyl ethyl ketone was added while stirring with a stirrer, and CB dispersion was performed. A liquid was prepared. In Example 2-1 of Table 3, the dispersant, the dispersion medium, and the addition amount of the dispersion medium are described.
〔実施例２−２〜２−７、比較例２−１〜２−６〕＜ＣＢ分散液または比較液の調製＞
表３に示す分散剤または比較剤と分散媒の組み合わせで、実施例２−１に準じて、実施例２−２〜２−７、比較例２−１〜２−６のＣＢ分散液および比較液を調製した。
[Examples 2-2 to 2-7, Comparative Examples 2-1 to 2-6] <Preparation of CB dispersion or comparative solution>
In accordance with Example 2-1, the CB dispersions of Comparative Examples 2-1 to 2-6 and Comparative Examples and Comparative Examples and Comparative Media and Dispersion Media shown in Table 3 were compared. A liquid was prepared.
〔参考例２〕＜ＣＢ分散液または比較液の分散媒添加量測定＞
ＣＢ分散液は、フロー値が２．３±０．１ｃｍになった点の分散媒添加量で調製した。ここで、フロー値とは、円状に広がった流動体の直径を指し、同じ値であれば流動性が同等であることを示す。フロー値の測定は以下のようにした。ディスポシリンジ（ＴＯＰ社製、容量５ｍＬ）の外筒を、先端から２ｃｍ程度のところで切断し、切断面開口部を上にして分散液２ｍＬを入れ、開口部を１０ｃｍ×１０ｃｍのガラス板で気体が入らないように塞ぎ、シリンジのピストン部分を固定しながらガラス板が下になるように上下反転させ、机上に置いた。最後に、シリンジの外筒を一気に引き上げ、ガラス板上に広がった円状の流動体の直径（フロー値）を測定した。
[Reference Example 2] <Measurement of amount of dispersion medium added to CB dispersion or comparative liquid>
The CB dispersion was prepared by adding a dispersion medium at a point where the flow value became 2.3 ± 0.1 cm. Here, the flow value refers to the diameter of the fluid spreading in a circular shape, and the same value indicates that the fluidity is equivalent. The flow value was measured as follows. Cut the outer cylinder of a disposable syringe (made by TOP Co., Ltd., capacity 5 mL) at about 2 cm from the tip, put 2 mL of dispersion liquid with the opening of the cut surface facing up, and open the opening with a glass plate of 10 cm × 10 cm. It was closed so as not to enter, and was fixed upside down so that the glass plate faced down while fixing the piston portion of the syringe, and placed on a desk. Finally, the outer cylinder of the syringe was pulled up at once, and the diameter (flow value) of the circular fluid spread on the glass plate was measured.
〔参考例３〕＜分散性評価１：ＣＢ分散液または比較液の分散媒添加量比較＞
分散媒添加量は、実施例では２０．０±３．２ｇ、比較例では２８．１±２．７ｇであり、実施例の分散液の方が、ＣＢが比較的高濃度でありながら、比較液と同じ流動性のスラリーが得られた。このことより、比較例より実施例の分散液の方がＣＢ分散性に優れていることが示された。
[Reference Example 3] <Dispersibility evaluation 1: Comparison of amount of dispersion medium added to CB dispersion or comparative liquid>
The addition amount of the dispersion medium is 20.0 ± 3.2 g in the example and 28.1 ± 2.7 g in the comparative example, and the dispersion liquid of the example has a comparatively high concentration of CB. A slurry having the same fluidity as the liquid was obtained. From this, it was shown that the dispersion liquid of an Example is more excellent in CB dispersibility than a comparative example.
〔参考例４〕＜分散性評価２：ＣＢ分散液または比較液の上層液吸光度測定＞
ＣＢ分散液または比較液を、遠心分離器（LEGEND MACH 1.6R、Kendro Laboratory 製）を用いて、10,000ｒｐｍ（9700ｇ）で３０分間遠心した。遠心後、上層液をデカンテーションにより採取し、５００ｎｍにおける吸光度を、光路長２ｍｍの石英セルで測定した。吸光度が高いほどＣＢが分散していることを示す。結果を表３に併せて示した。この結果、上層液の吸光度は、実施例が１. ９２３ｎｍ以上、比較例が０．０１４〜０．０２１ｎｍであり、実施例の方が高い値であった。以上より、実施例の分散液はＣＢ分散性に優れていることが示された。
[Reference Example 4] <Dispersibility Evaluation 2: CB Dispersion or Comparative Solution Upper Layer Absorbance Measurement>
The CB dispersion or comparative solution was centrifuged at 10,000 rpm (9700 g) for 30 minutes using a centrifuge (LEGEND MACH 1.6R, manufactured by Kendro Laboratory). After centrifugation, the upper layer liquid was collected by decantation, and the absorbance at 500 nm was measured with a quartz cell having an optical path length of 2 mm. The higher the absorbance, the more CB is dispersed. The results are also shown in Table 3. As a result, the absorbance of the upper layer liquid was 1.923 nm or more in the example and 0.014 to 0.021 nm in the comparative example, and the value of the example was higher. As mentioned above, it was shown that the dispersion liquid of an Example is excellent in CB dispersibility.
〔実施例２−１〜２−７、比較例２−１〜２−６〕＜ＣＢ分散液または比較液のろ液調製＞
実施例２−１〜２−７、比較例２−１〜２−６で作製したＣＢ分散液または比較液を、分散媒で１０倍に希釈した。その希釈液をろ紙（５Ａ、東洋濾紙（株）製）にてろ過し、ろ液を調製した。
[Examples 2-1 to 2-7, Comparative Examples 2-1 to 2-6] <Preparation of CB dispersion or filtrate of comparative solution>
The CB dispersions or comparative solutions prepared in Examples 2-1 to 2-7 and Comparative Examples 2-1 to 2-6 were diluted 10 times with a dispersion medium. The diluted solution was filtered with a filter paper (5A, manufactured by Toyo Filter Paper Co., Ltd.) to prepare a filtrate.
〔参考例５〕＜分散性評価３：ＣＢ分散液または比較液のろ液評価＞
ろ液のＣＢ分散性を目視にて評価した。ろ液の色は、黒色が濃いほどＣＢ分散性が優れていることを示す。評価結果を表３に併せて示した。この結果、ろ液の色は、実施例が◎（黒色）または○（薄黒色）、比較例が×（無色透明）であった。以上より、実施例のろ液はＣＢを含有しており、ＣＢ分散性に優れていることが示された。
[Reference Example 5] <Dispersibility Evaluation 3: Evaluation of Filtrate of CB Dispersion or Comparative Solution>
The CB dispersibility of the filtrate was visually evaluated. The color of the filtrate indicates that the darker the black, the better the CB dispersibility. The evaluation results are also shown in Table 3. As a result, the color of the filtrate was ◎ (black) or ◯ (light black) in Examples, and × (colorless and transparent) in Comparative Examples. As mentioned above, it was shown that the filtrate of an Example contains CB and is excellent in CB dispersibility.
〔実施例３−１〕＜ＣＮＦ分散液の調製＞
トルエン１００．０ｇに実施例１−１の分散剤１．０ｇを溶解後、ＣＮＦ（ＶＧＣＦ−Ｈ、昭和電工（株）製）０．２ｇを添加し、スターラーで１時間攪拌後、超音波照射器（Ultrasonic Generator Model ＵＳ−１５０、（株）日本精機製作所製）を用いて約１時間超音波照射することで、ＣＮＦ分散液を調製した。なお、超音波照射時は、液の発熱を抑えるために、適宜、氷水等で冷却し、液温を４０℃以下に保持した。表４の実施例３−１に、分散剤、被分散物および分散媒を記した。
[Example 3-1] <Preparation of CNF dispersion>
After dissolving 1.0 g of the dispersant of Example 1-1 in 100.0 g of toluene, 0.2 g of CNF (VGCF-H, manufactured by Showa Denko KK) was added, stirred for 1 hour with a stirrer, and then irradiated with ultrasonic waves. A CNF dispersion was prepared by irradiating ultrasonically for about 1 hour using a container (Ultrasonic Generator Model US-150, manufactured by Nippon Seiki Seisakusho Co., Ltd.). In addition, in order to suppress the heat_generation | fever of a liquid at the time of ultrasonic irradiation, it cooled with ice water etc. suitably and the liquid temperature was kept at 40 degrees C or less. In Example 3-1, Table 4, the dispersant, the dispersion, and the dispersion medium were described.
〔実施例３−２〜３−５、比較例３−１〜３−２〕＜ＣＮＦ、ＣＮＴ分散液または比較液の調製＞
表４に示す分散剤または比較剤、被分散物、分散媒の組み合わせで、実施例３−１に準じて、実施例３−２〜３−５、比較例３−１〜３−２のＣＮＦ、ＣＮＴ分散液または比較液を調製した。
[Examples 3-2 to 3-5, Comparative Examples 3-1 to 3-2] <Preparation of CNF, CNT dispersion or comparative solution>
A combination of a dispersant or a comparative agent, a dispersion, and a dispersion medium shown in Table 4, according to Example 3-1, Examples 3-2 to 3-5 and CNFs of Comparative Examples 3-1 to 3-2 A CNT dispersion liquid or a comparative liquid was prepared.
〔参考例６〕＜分散性評価４：ＣＮＦ、ＣＮＴ分散液または比較液の上層液吸光度測定＞
ＣＮＦ、ＣＮＴ分散液または比較液の上層液吸光度を、参考例４と同様の方法で測定した。吸光度が高いほどＣＮＦまたはＣＮＴが分散していることを示す。結果を表４に併せて示した。この結果、上層液の吸光度は、ＣＮＦでは、実施例が０．５２６〜１．８２６ｎｍ、比較例が０．０１８ｎｍ、ＣＮＴでは、実施例が１０ｎｍより大きく、比較例が０．０１６ｎｍとなり、ＣＮＦ、ＣＮＴともに実施例の方が高い値であった。以上より、実施例の分散液はＣＮＦ、ＣＮＴ分散性に優れていることが示された。
[Reference Example 6] <Dispersibility evaluation 4: CNF, CNT dispersion or comparative liquid upper layer absorbance measurement>
The absorbance of the upper layer solution of CNF, CNT dispersion or comparative solution was measured by the same method as in Reference Example 4. The higher the absorbance, the more CNF or CNT is dispersed. The results are also shown in Table 4. As a result, the absorbance of the upper layer liquid was 0.526 to 1.826 nm for the CNF example, 0.018 nm for the comparative example, and greater than 10 nm for the CNT example and 0.016 nm for the comparative example. The value of Example was higher for both CNTs. As mentioned above, it was shown that the dispersion liquid of an Example is excellent in CNF and CNT dispersibility.
〔実施例３−１〜３−５、比較例３−１〜３−２〕＜ＣＮＦ、ＣＮＴ分散液または比較液のろ液調製＞
実施例３−１〜３−５、比較例３−１〜３−２で調製したＣＮＦ、ＣＮＴ分散液または比較液を、分散媒で１０倍に希釈した。その希釈液をろ紙（５Ａ、東洋濾紙（株）製）にてろ過し、ろ液を調製した。また、実施例３−３〜３−５で調製したＣＮＴ分散液については、分散媒で１００倍に希釈した希釈液のろ液も調製した。
[Examples 3-1 to 3-5, Comparative Examples 3-1 to 3-2] <CNF, CNT dispersion or comparative filtrate preparation>
The CNF, CNT dispersion liquid or comparative liquid prepared in Examples 3-1 to 3-5 and Comparative Examples 3-1 to 3-2 was diluted 10 times with a dispersion medium. The diluted solution was filtered with a filter paper (5A, manufactured by Toyo Filter Paper Co., Ltd.) to prepare a filtrate. Moreover, about the CNT dispersion liquid prepared in Examples 3-3 to 3-5, the filtrate of the dilution liquid diluted 100 times with the dispersion medium was also prepared.
〔参考例７〕＜分散性評価５：ＣＮＦ、ＣＮＴ分散液または比較液のろ液評価＞
ろ液のＣＮＦ、ＣＮＴ分散性を目視にて評価した。ろ液の色は、黒色が濃いほどＣＮＦ、ＣＮＴ分散性が優れていることを示す。評価結果を表４に併せて示した。この結果、１０倍希釈のろ液の色は、ＣＮＦでは実施例が○（薄黒色）、比較例が×（無色透明）であり、ＣＮＴでは実施例が◎（黒色）、比較例が×（無色透明）であった。また、１００倍希釈液のろ液の色は、実施例３−５が◎（黒色）、実施例３−４および３−５が○（薄黒色）であった。以上より、実施例のろ液はＣＮＦ、ＣＮＴを含有しており、ＣＮＦ、ＣＮＴ分散性に優れていることが示され、特に実施例３−５がＣＮＴ分散性に優れていることが示された。
[Reference Example 7] <Dispersibility evaluation 5: Evaluation of filtrate of CNF, CNT dispersion or comparative liquid>
The CNF and CNT dispersibility of the filtrate was visually evaluated. The darker the color of the filtrate, the better the CNF and CNT dispersibility. The evaluation results are also shown in Table 4. As a result, the color of the filtrate diluted 10-fold is ○ (light black) in the case of CNF and × (colorless and transparent) in the comparative example, and ◎ (black) in the example of CNT and × ( Colorless and transparent). Moreover, Example 3-5 was (circle) (black), and Example 3-4 and 3-5 were (circle) (light black) about the color of the filtrate of a 100 times dilution liquid. From the above, it is shown that the filtrate of the example contains CNF and CNT, and is excellent in CNF and CNT dispersibility, and in particular, Example 3-5 is excellent in CNT dispersibility. It was.
〔実施例４−１〕＜ＣＢ分散液からの炭素材料組成物の調製＞
表３に示す実施例２−１のＣＢ分散液を、４０℃以下でエバポレーションし、溶媒を除去した。溶媒除去後、粉砕し、炭素材料が分散剤で被膜された炭素材料組成物を得た。
[Example 4-1] <Preparation of carbon material composition from CB dispersion>
The CB dispersion of Example 2-1 shown in Table 3 was evaporated at 40 ° C. or lower to remove the solvent. After removing the solvent, the mixture was pulverized to obtain a carbon material composition in which the carbon material was coated with a dispersant.
〔実施例４−２〜４−１２、比較例４−１〜４−８〕＜ＣＢ、ＣＮＦ、ＣＮＴ分散液または比較液からの炭素材料組成物の調製＞
実施例４−１に準じて、実施例４−２〜４−１２、比較例４−１〜４−８の炭素材料が分散剤または比較剤で被膜された炭素材料組成物を得た。
[Examples 4-2 to 4-12, Comparative examples 4-1 to 4-8] <Preparation of carbon material composition from CB, CNF, CNT dispersion liquid or comparison liquid>
In accordance with Example 4-1, carbon material compositions in which the carbon materials of Examples 4-2 to 4-12 and Comparative Examples 4-1 to 4-8 were coated with a dispersant or a comparative agent were obtained.
〔実施例５−１〕＜ＣＢ再分散液のろ液調製＞
実施例４−１の炭素材料組成物に、メチルエチルケトンを２２．４ｇ添加し、スターラーで１時間攪拌してＣＢ再分散液を調製し、分散媒で１０倍に希釈した。その希釈液をろ紙（５Ａ、東洋濾紙（株）製）にてろ過し、ろ液を調製した。表５の実施例５−１に、炭素材料組成物、分散媒および分散媒添加量を記した。
[Example 5-1] <Preparation of CB redispersion filtrate>
To the carbon material composition of Example 4-1, 22.4 g of methyl ethyl ketone was added and stirred with a stirrer for 1 hour to prepare a CB redispersion liquid, which was diluted 10 times with a dispersion medium. The diluted solution was filtered with a filter paper (5A, manufactured by Toyo Filter Paper Co., Ltd.) to prepare a filtrate. In Example 5-1 of Table 5, the carbon material composition, the dispersion medium, and the addition amount of the dispersion medium are described.
〔実施例５−２〜５−７、比較例５−１〜５−６〕＜ＣＢ再分散液、比較液のろ液調製＞
表５に示す炭素材料組成物、分散媒、添加量の組み合わせで、実施例５−１に準じて、実施例５−２〜５−７、比較例５−１〜５−６のＣＢ再分散液、比較液のろ液を調製した。
[Examples 5-2 to 5-7, Comparative examples 5-1 to 5-6] <CB redispersion and preparation of filtrate of comparative solution>
CB redispersion in Examples 5-2 to 5-7 and Comparative Examples 5-1 to 5-6 in accordance with Example 5-1 with combinations of carbon material compositions, dispersion media, and addition amounts shown in Table 5 And a filtrate of a comparative solution were prepared.
〔実施例５−８〕＜ＣＮＦ再分散液のろ液調製＞
実施例４−８の炭素材料組成物に、トルエン１００. ０ｇを添加し、スターラーで１時間攪拌後、超音波照射器を用いて約１時間超音波照射してＣＮＦ再分散液を調製し、分散媒で１０倍に希釈した。その希釈液をろ紙（５Ａ、東洋濾紙（株）製）にてろ過し、ＣＮＦ再分散液のろ液を調製した。なお、超音波照射時は、液の発熱を抑えるために、適宜、氷水等で冷却し、液温を４０℃以下に保持した。表５の実施例５−８に、炭素材料組成物、分散媒および分散媒添加量を記した。
[Example 5-8] <Preparation of CNF redispersion filtrate>
To the carbon material composition of Example 4-8, 100.0 g of toluene was added, stirred for 1 hour with a stirrer, and then ultrasonically irradiated with an ultrasonic irradiator for about 1 hour to prepare a CNF redispersion liquid, It was diluted 10 times with a dispersion medium. The diluted solution was filtered with a filter paper (5A, manufactured by Toyo Filter Paper Co., Ltd.) to prepare a CNF redispersion filtrate. In addition, in order to suppress the heat_generation | fever of a liquid at the time of ultrasonic irradiation, it cooled with ice water etc. suitably and the liquid temperature was kept at 40 degrees C or less. In Example 5-8 of Table 5, the carbon material composition, the dispersion medium, and the addition amount of the dispersion medium are described.
〔実施例５−９〜５−１２、比較例５−７〜５−８〕＜ＣＮＦ、ＣＮＴ再分散液または比較液のろ液調製＞
表５に示す炭素材料組成物、分散媒、添加量の組み合わせで、実施例５−８に準じて、実施例５−９〜５−１２、比較例５−７〜５−８のＣＮＦ、ＣＮＴ再分散液または比較液のろ液を調製した。また、実施例５−１０〜５−１２で調製したＣＮＴ分散液については、分散媒で１００倍に希釈した希釈液のろ液も調製した。
[Examples 5-9 to 5-12, Comparative Examples 5-7 to 5-8] <CNF, CNT redispersion liquid or comparison liquid filtrate preparation>
CNFs and CNTs of Examples 5-9 to 5-12 and Comparative Examples 5-7 to 5-8 according to Example 5-8, with combinations of carbon material compositions, dispersion media, and addition amounts shown in Table 5 A re-dispersion or comparative filtrate was prepared. Moreover, about the CNT dispersion liquid prepared in Examples 5-10 to 5-12, the filtrate of the dilution liquid diluted 100 times with the dispersion medium was also prepared.
〔参考例８〕＜分散性評価６：ＣＢ、ＣＮＦ、ＣＮＴ再分散液または比較液のろ液評価＞
ろ液のＣＢ、ＣＮＦ、ＣＮＴ分散性を目視にて評価した。ろ液の色は、黒色が濃いほどＣＢ、ＣＮＦ、ＣＮＴ分散性が優れていることを示す。評価結果を表５に併せて示した。この結果、再分散液は〔参考例５〕、〔参考例７〕のろ液と同等の結果が得られ、炭素材料組成物を再分散させた分散液も分散性に優れていることが示された。
[Reference Example 8] <Dispersibility evaluation 6: Evaluation of filtrate of CB, CNF, CNT redispersion liquid or comparative liquid>
The CB, CNF, and CNT dispersibility of the filtrate was visually evaluated. The color of the filtrate indicates that CB, CNF, and CNT dispersibility are better as the black color is darker. The evaluation results are also shown in Table 5. As a result, the redispersion liquid obtained the same results as the filtrates of [Reference Example 5] and [Reference Example 7], and it was shown that the dispersion liquid obtained by redispersing the carbon material composition is also excellent in dispersibility. It was done.
本発明によって、炭素材料を有機溶媒中で均一かつ安定に分散することができる分散剤や組成物を提供できるので、本発明の分散剤や組成物は印刷用着色剤、導電性材料、電子関連材料、建築用構造材、自動車用外装部品への静電塗装材料、工業用包装材料、電磁波シールド材料などへの利用が可能となる。 Since the present invention can provide a dispersant or composition that can uniformly and stably disperse a carbon material in an organic solvent, the dispersant or composition of the present invention can be used as a printing colorant, a conductive material, and an electronic material. It can be used for materials, construction materials for construction, electrostatic coating materials for automobile exterior parts, industrial packaging materials, electromagnetic shielding materials, and the like.
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